Cryogenic nitrogen rejection from methane-rich natural gas is a critical operation for meeting LNG and pipeline gas specifications. Yet, it is highly susceptible to operational disturbances caused by solid formation in heat exchangers and distillation columns. This study proposes an integrated simulation framework that couples steady-state process modeling in Aspen HYSYS with rigorous solid–liquid–vapor equilibrium (SLVE) analysis in ThermoFAST to evaluate freezing risks in CH4 systematically–N2 mixtures under nitrogen-rejection unit (NRU) conditions. The NRU process, including multi-stream heat exchange, Joule–Thomson expansion, and cryogenic distillation, is modeled using the Peng–Robinson equation of state. ThermoFAST employs a Helmholtz-energy-based PC-SAFT equation of state, together with Lennard-Jones Weeks–Chandler–Andersen (LJ-WCA) pure-solid references, to generate freezing envelopes over a wide pressure range (0.1–10 MPa) and across methane-rich to nitrogen-rich compositions relevant to industrial operations.

The framework is validated against available experimental solid–liquid equilibrium data, yielding mean absolute and relative deviations of 3.45 K and 5%, respectively, demonstrating its suitability for hazard screening applications. Simulation results reveal that increasing pressure elevates the eutectic temperature and expands the stability region of the solid phase. In contrast, increasing nitrogen concentration depresses the eutectic point and narrows the solid stability range. Risk maps indicate that solid formation is most probable in methane-rich streams (CH4 > 0.75) at pressures of 10 MPa or higher, as well as in nitrogen-rich streams (CH4 < 0.55) at extremely low temperatures, particularly after expansion and in the upper trays of the distillation column. The proposed integrated approach provides a predictive tool for identifying vulnerable operating zones, defining safe temperature–pressure margins, and enhancing the safety, operability, and efficiency of cryogenic nitrogen rejection processes.